Loyola College M.Sc. Chemistry April 2016 Applied Organic Chemistry Question Paper PDF Download

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Loyola College M.Sc. Chemistry Nov 2016 Main Group Elements & Nuclear Chemistry Question Paper PDF Download

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Loyola College M.Sc. Chemistry April 2003 Structural Inorganic Chemistry Question Paper PDF Download

LOYOLA  COLLEGE (AUTONOMOUS), CHENNAI-600 034.

M.Sc. DEGREE  EXAMINATION  – chemistry

first  SEMESTER  – APRIL 2003

CH  1802/CH 719  structural inorganic chemistry

08.04.2002

1.00 – 4.00                                                                                          Max: 100 Marks

 

PART A                                                     (10 ´ 2 = 20 Marks)

Answer the following

  1. Mention one example each for spinel and inverse spinel.
  2. Mention coordination numbers in fluorite and antifluorite structures.
  3. Suggest a technique to study the following

(a) hydrogen bonding in ice  (b) bond length in diborane.

  1. ZnO acts as a n- type semiconductor.
  2. Predict the structure of B4 H10 applying Wades Rules.
  3. What is radius ratio? What is its significance?
  4. Taking H2 molecule as example show how molecular orbitals are obtained?
  5. How are n and p-type extrinsic semiconductors prepared?
  6. Explain van der Waal’s forces.
  7. What are gas hydrates and clathrates? Cite examples.

 

PART B                                                          (8 ´ 5 = 40 Marks)

Answer any eight of the following

  1. Discuss and compare the structures of Wurtzite and Zinc blende.
  2. How are silicates prepared? Mention their applications.
  3. How are metallocarboranes prepared?
  4. Mention the advantages of single crystal X-ray diffraction analysis.
  5. Write a note on Schottky and Frenkel defects.
  6. How is structure factor derived for an array of atoms in a crystal lattice?
  7. What is Madelung constant? Calculate this constant for NaCl crystal

(first two terms only)

  1. How is lattice energy calculated using Born-Haber cycle?
  2. Discuss factors which influence hard/soft nature of cations.
  3. Construct MO diagram for NO molecule and explain its magnetic property and stability.
  4. Arrange the following molecules according to increasingbond angles.

Give reason(s) (i)  CH4  (ii) CH2F2   (iii)  CH2I2.

 

 PART C                                                     (4 ´10= 40 Marks)

Answer any four of the following

  1. How are phosphonitric compounds prepared?

Discuss the structure of P3 N3 Cl6.

  1. Discuss the following structures and draw silicate units:

(i) beryl        (ii) talc  (iii) quartz (iii) pyrosilicate           (3+3+2+2)

  1. Discuss structures of spinels and inverse spinels taking Mn3 O4as typical examples.
  2. Explain Fajan’s Rules with suitable examples.
  3. Using band theory discuss conductance properties of (i) Mg (I)Hg (iii) I2    (3+3+4)
  4. Write an essay on non-equeous solvents and their applications.

 

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Loyola College M.Sc. Chemistry April 2003 Science & Society Question Paper PDF Download

LOYOLA  COLLEGE (AUTONOMOUS), CHENNAI-600 034.

M.Sc. DEGREE  EXAMINATION  – chemistry

second SEMESTER  – APRIL 2003

CH  2803/CH 820  science and society

28.04.2002

1.00 – 4.00                                                                                          Max: 100 Marks

 

PART A                                                     (10 ´ 2 = 20 Marks)

Answer the following

  1. How do scientific results reach society for development?

02.      Write notes on (i) transfer of technology  and (ii)  transformation of technology.

  1. How is acid rain caused?
  2. What is meant by equilibrium of ecology?
  3. Cite advantages and disadvantages in using robots.
  4. What is meant by drug abuse? Cite one specific example.
  5. Why do scientists make assumptions?
  6. What are the promises and perils in using genetic engineering?
  7. Explain the terms (i) information and (ii)   disinformation
  8. Describe ‘cost effectiveness of scientific research’.

 

PART B                                         (4 ´ 10 = 40 Marks)

Answer any four of the following

  1. How does scientific development influence culture of a society?
  2. What are the reasons for environmental degradation?
  3. ‘Science is not against religious sentiments’ –
  4. What is industrialization of science? What is its significance?
  5. Discuss the role of scientists as bridge between industries and ecology.
  6. Why do some biological species vanish from world? Is this change desireable always?

PART C                                          (2 ´ 20 = 40 Marks)

Answer any TWO of the following.

  1. Write an essay on planning a research project and its successful completion.
  2. Make a comparitive study on scientific development in rural and urban areas.
  3. What are advantages, disadvantages and threats in using computers and internet for scientific research?

 

  1. Analyse pros and cons of non-conventional energy sources, with special

reference to nuclear energy and solar energy.

 

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Loyola College M.Sc. Chemistry April 2003 General Chemistry For Maths & Physics Question Paper PDF Download

LOYOLA  COLLEGE (AUTONOMOUS), CHENNAI-600 034.

M.Sc. DEGREE  EXAMINATION  – chemistry

fourth  SEMESTER  – APRIL 2003

CH  4200/CHE 200 general chemistry for maths & physics

22.04.2002

9.00 – 12.00                                                                                    Max: 100 Marks

 

 

PART A                (10 ´ 2 = 20 Marks)

                                                  Answer ALL the questions.

  1. Define Lattice energy.
  2. State Kohlrausch’s law.
  3. Draw the structure of glucose.
  4. How does a – amino acid exist in acidic medium and alkaline medium?
  5. What is Bordeaux mixture? What is it used for?
  6. Mention two applications of radio isotopes in medicine.
  7. What are antipyretics? Give one example.
  8. What happens when anthracene is brominated?
  9. What are mordants?
  10. Acetic acid in benzene exists as a dimer –

           PART – B                               (8 ´ 5 = 40 Marks)

                                             Answer any EIGHT questions

  1. Write a note on carcinogenic hydrocarbon.
  2. How is congo red prepared?
  3. Explain the mode of action of sulpha drug.
  4. How is anthracene isolated from coal tar?
  5. How are the following prepared?

(i)   Malachite green     (ii) aspirin

  1. Derive Kirchoff’s equation
  2. Draw the conductometric titration curves for the following and explain.

(i)  HCl  vs NaOH                 (ii)  CH3 COOH Vs NaOH

  1. Discuss the factors affecting enzyme catalysis.
  2. Write a note on photosynthesis.
  3. Explain the features of nuclear fission reaction.
  4. Explain the construction of calomel electrode. What is the electrode reaction?

           

 

 

 

 

PART – C                                       (4 ´ 10 = 40 Marks)

                                     Answer any FOUR questions

 

  1. Construct Born Haber cycle for NaCl(s). Mention the terms involved.
  2. a) Discuss the primary structure of proteins.                                                       (5)
  3. b) Write a note on herbicides                                                                              (5)
  4. a) Explain the role of micro-nutrients in the growth of  plants                          (5)
  5. b) What is the role of enzyme in enzyme catalysis?                                           (5)
  6. How is the dissociation constant of acetic acid determined using conductivity measurement?
  7. a)  How are lanthanides separated by ion-exchange method?                             (6)
  8. Physical properties of compounds are affected by H-bonding – Explain

with two examples.                                                                                         (4)

  1. a) What are chromophores and auxochromes?  Give examples.              (5)
  2. How are the following conversions effected?

(i)pyrrole to 2-nitro pyrrole.  (ii)   Pyrrole to Pyrolle-2-aldehyde                 (5)

 

 

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Loyola College M.Sc. Chemistry April 2003 Advanced Coordination Chemistry Question Paper PDF Download

 

 

LOYOLA  COLLEGE (AUTONOMOUS), CHENNAI-600 034.

M.Sc. DEGREE  EXAMINATION  – chemistry

fourth  SEMESTER  – APRIL 2003

CH  4950/CH 1054 ADVANCED COORDINATION  chemistry 

23.04.2002

1.00 – 4.00                                                                                          Max: 100 Marks

 

part A                                                       (10 ´ 2 = 20)

 

  1. What is slipped Sandwich?   Cite an example.
  2. Define coordination template effect. Cite a dinuclear complex synthesized by

the method.

  1. Justify the formation of coordination compounds of different geometries by d-

block metal ion with the help of angular overlap model.

  1. What is tetragonal splitting parameter? How is it evaluated?
  2. Differentiate CE and EC mechanisms.
  3. Give the structure of (a) Potassium ethylxanthate

(b) Dipheylphosphinoethane (dppe).

  1. How are he optical isomers of [Co (NH3)4 Cl2]+ distinguished?
  2. [NiCl4]2- has a magnetic moment of 2.84 B.M. Predict the geometry with hybridization of the metal atom.
  3. How are the complexes [Cr(NH3]4 Cl2]Cl and [Cr(NH3)3Cl3] distinguished by NQR spectroscopy?
  4. What role is  played by cisplatin in the cancer therapy?

 

PART- B                                           (8 ´ 5 = 40 Marks)

 

  1. Explain the principles of angular overlap model.
  2. What are compartmental ligands? Explain the different methods of syntheizing compartmental ligands and their polynuclear complexes.
  3. Explain the electronic spectral features of high-spin octahedral and tetrahedral complexes.
  4. Give an account of spectroelectrochemical techniques in studying electrogenerated species.
  5. Explain the principle of AC polarography. How is this technique useful to study the reversible redox couples?
  6. Explain with an example the experimental method of studying static dynamic Jahn-Teller effect.
  7. Explain that the isomer shift value of [Fe (CN)6]4 is more negative than that of

[Fe (H2O)6]2+ . D EQ of the former is zero and the later has a D EQ value of 3.3 mm s-1.

 

 

 

 

 

  1. Suggest a method of synthesis for

(a) [Co (NH3)6]Cl3 from CoCl2.6H2O                                                                                     (2)

(b) Cis and trans – [Pt(NH3)2Cl2]                                                               (1 ½  + 1 ½)

 

  1. Discuss the different sampling methods used in EPR spectroscopy. Bring out their advantages.
  2. How do the quantum yields vary in a photoanation reactions? Discuss with a suitable example.
  3. Discuss the coordination around iron in cytochrome and the role played by it in the biological processes.
  4. How is N(1s) photoelectron spectrum useful in the study of [Co(NH3)5 N3](NO3)2

 

PART – C                                         (4 ´10 = 40 Marks)

 

  1. (a) Derive the Marcus-Hush equation for electron transfer.
  • Explain how do the crystal field effect influence the rate of electron

transfer reactions.

  1. (a) Explain the electronic spectral features of  low -spin d6 metal ion and

the  method of computing Dqxy and Dqz values.

  • How is spin crossover studied experimentally?
  • Give an account of NMR spectra of paramagnetic compounds.

 

  1. Discuss the role played by the metal atoms in the Nitrogen fixation. Write a note

on  biomimic coordination. cluster complexes of nitrogenase.

 

  1. (a) Explain the  Mossbauer spectrum of FeF3 recorded at 4K.                         (5)
  • Describe Krammer’s degeneracy choosing an example.

 

  1. (a) Discuss in detail the EPR spectrum of [Cu (salimine)2] along with the

hyperfine splitting by the ligand.                                                                 (7)

 

(b)   How does Cr(CO)6 undergo photochemical decomposition?                      (3)

 

 

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Loyola College M.Sc. Chemistry Nov 2003 Thermodynamics & Statistical Mechanics Question Paper PDF Download

LOYOLA COLLEGE (AUTONOMOUS), CHENNAI –600 034

M.Sc., DEGREE EXAMINATION – CHEMISTRY

 SECOND SEMESTER – NOVEMBER 2003

CH-2800/815  – THERMODYNAMICS & STATISTICAL MECHANICS

28-10-2003                                                                                                     Max:100 marks

1.00 – 4.00

 

PART – A                                           (10×2=20 marks)

Answer ALL questions.

 

  1. If V = for 1mole of an ideal gas show that dV is a complete differential.
  2. Kp for the reaction at 500oC is 3.99×10-3 atm-1 Calculate DGo for the reaction.
  3. Show that .
  4. What is chemical potential? Is it extensive or intensive?
  5. How many components are present in a system in which NH4Cl (s) undergoes thermal decomposition?
  6. Calculate the number of ways of distributing 20 identical objects with the arrangement 1, 0, 3, 5, 10, 1.’
  7. What is the significance of partition function?
  8. What is the residual molar entropy of CO at T = O?
  9. Identify the systems for which it is essential to include a factor of on going from molar partition function to molecular partition function a) a sample of CO2 (g) b) water vapour.
  10. Calculate the ratio of the translation partition functions of D2 and H2 at the same temperature and pressure.

 

PART – B                                           (8×5=40 marks)

Answer any EIGHT questions.

 

  1. Derive expressions for isothermal reversible expansion of 1 mol of Vander Waal’s gas for a) W b) D
  2. DS of a solid in cal/k/mole is given by the equation Cp = 6.2 + 1.3 x 10-3T in the temperature range 27oC to 600o Calculate DS when 1 mole of this metal is heated from 300 k to 600 k.
  3. Derive any two Maxwell equations.
  4. The volume of an aqueous soltuon of NaCl at 25oC was measured in series of molalities (m) and it was found that the volume fitted the expression

V (CC) = 1003 + 16.62m + 1.77 m3/2 + 0.km2 where V is the volume of a solution of molality 1.  Calculate the partial molar volume of a the components in a solution of molality 0.1.

  1. 325 g of N2O4 when heated was found to occupy a volume of 500 ml at 45oC and at 800 mm Hg pressure Calculate i) Kp ii) pressure at which the degree of dissociation is 50%.
  2. Explain how partition functions can be separated.
  3. Calculate the standard molar entropy of Xenon gas at 100 K.
  4. Calculate the electronic partition function of a Tellurium atom at 500 K using the following data.

Term                Degeneracy                 Wave number (cm-1)

 

Ground                 5                                     0

1                      1                                   4707

2                      3                                   4751

3                      5                                 10559

  1. Explain how the absolute entropy of a gas at 25oC can be determined using third law of thermodynamics.
  2. Compare Maxwell – Bolltzmann, Fermi – Dirac and Bose – Einstein statistical distributions.
  3. Calculate the molecular rotational partition function for N2 (g) at 27o

(I = 13.9 x 10-47 kgm-2).

  1. Derive an expression for transnational partition function.

 

 

PART – C                                           (4×10=40 marks)

Answer any FOUR questions.

 

  1. a) Derive Gibbs – Duhem equation.
  2. b) Show that for 1 mole of a van der waal’s gas.
  3. a) Explain how activity coefficient of an electrolyte be determined using EMF data.
  4. b) Derive thermodynamically phase rule equation.
  5. a) The virial equation of state for N2(g) at OoC is

PV = RT – 1.051 x10-2 P + 8.63 x 10-5 P2 + ….

Where P is in atm; V is in litres.  Find the fugacity of N2 at OoC and 100 atm.

pressure.

  1. b) Deduce the expression for the variation of chemical potential with i) temperature ii)

pressure.

  1. State the postulates of Maxwell – Boltzmann statistics and hence derive an expression for the most probable distribution.
  2. Compare Einstein’s theory of heat capacity of solids with Debye’s theory.
  3. a) Explain how equilibrium constant of a reaction be obtained using statistical mechanics.
  4. b) Explain transition state theory using statistical concepts.
  5. a) Derive the relation

E = .

  1. b) Calculate the vibrational contribution to the entropy of Cl2 at 500K if the wave

number of the vibration is 560 cm-1.

 

 

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Loyola College M.Sc. Chemistry Nov 2003 Electrochemistry Question Paper PDF Download

LOYOLA COLLEGE (AUTONOMOUS), CHENNAI –600 034

M.Sc., DEGREE EXAMINATION – CHEMISTRY

 FOURTH SEMESTER – NOVEMBER 2003

CH – 4803/1020 –  ELECTRO CHEMISTRY

01-11-2003                                                                                                     Max:100 marks

1.00 – 4.00

 

PART – A                                           (10X2=20 marks)

Answer ALL questions.

 

  1. The limiting molar conductance of OHis highest among the anions – Explain.
  2. Calculate the ionic strength of a mixture containing 20 mL of 0.1M lanthanum sulphate, 30 mL of 0.5 M magnesium nitrate and 50 mL of water.
  3. In case of alkali halides the deviation from Debye Huckel Onsager equation is more marked as the atomic weight increases – Explain.
  4. Calculate the limiting molar conductance of lanthanum ion if its mobility is 7.21 x 10-8 m2 V-1 S-1.
  5. Write Lippmann’s first equation and mention its importance.
  6. Draw the plot of current density vs applied potential for an electrolytic solution and hence indicate the discharge potential of an ion.
  7. Mention the electrical properties that influence the rate of an electrochemical reaction.
  8. Bring out the differences between symmetry factor and transfer coefficient.
  9. What do you mean by non-polarisable electrode?
  10. Define exchange current density.

 

PART – B                                           (8X5=40 marks)

Answer any EIGHT questions.

 

  1. Calculate the instability constant of the complex formed in the reaction

Cu+2 + 4 NH3        [Cu (NH3)4]+2

Given Cu+2 +2  Cu(s)                                       Eo = 0.337 V

[Cu (NH3)4]2+ + 2    Cu(s)  + 4 NH3                Eo = -0.12 V.

  1. 2 M lead nitrate solution freezes at -0.05oC. Calculate its dissociation constant.  Cryoscopic constant of water is 1.86 kg K mol-1.
  2. The dissociation constant of chloroacetic acid is 1 x 10-4. Will the degree of dissociation increase or decrease if 0.1 M KCl is added to 0.1 M chloro acetic acid?
  3. Write notes on electro kinetic phenomena.
  4. Discuss electrocapillary phenomena.
  5. How is the limiting molar conductance of acetic acid determined using Debye Huckel Onsager – equation?
  6. Compare the rates of reduction of Ag+, at over voltages -0.1 and +0.1 V, which has a symmetry factor, = 0.5.
  7. Explain any one experimental method of determining the exchange current density.
  8. State Butler – volmer equation for one electron process. Derive Nernst equation from it.
  9. Determine the order of the reaction 2 H3O+ + 2e 2 H2O + H2 in acidic medium.
  10. Derive Tafel equation for cathodic process.
  11. Define half wave potential. Show that it is a constant characteristic of the electro active species.

 

 

PART – C                                           (4X10=40 marks)

Answer any FOUR questions.

 

  1. State the postulates of Debye Huckel theory and derive an expression for Debye Huckel length.
  2. Derive Debye Huckel limiting law. How is it verified?  Mention its applications.
  3. What are the features of Helmholtz Perrin model? What are its limitations?  How are these overcome in Stern’s model?
  4. a) Derive the Butler – Volmer equation for a multistep electrochemical reaction.
  5. b) Explain the condition under which the above equation reduces to simpler Butler –

Volmer equation.

  1. a) A cathodic potential of 3V is applied to Cu2+ and Na+ solutions separately.  Calculate

the over potential of the two electrodes.

  1. b) Explain any three applications of polarography.
  2. a) Obtain an expression for limiting current on the basis of concentration polarization.
  3. b) Write a note on
  4. Cyclic voltametry
  5. Amperometric titrations

 

 

 

 

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Loyola College M.Sc. Chemistry Nov 2003 Analytical Chemistry Question Paper PDF Download

LOYOLA COLLEGE (AUTONOMOUS), CHENNAI –600 034

M.Sc., DEGREE EXAMINATION – CHEMISTRY

THIRD SEMESTER – NOVEMBER 2003

CH – 3805/924 – ANALYTICAL CHEMISTRY

10-11-2003                                                                                                     Max:100 marks

1.00 – 4.00

 

PART – A

Answer ALL the questions.                                                                              (10×2=20 marks)

 

  1. Explain constant error with an example.
  2. Ce+4 + Ce+3   Eo = 1.44 V

Sn+4 + 2         Se+2   Eo = 0.15 V

Compute the equivalence point potential for the above system.

  1. Explain replacement titration with an example.
  2. Mention the factors which affect the pM value at the equivalence point.
  3. Calculate the equivalence point pH when 20.00 mL of 0.1000 M CH3 COOH is titrated against 0.2000M NaOH (Ka for CH3 COOH 1 x 10-5)
  4. How will you estimate phenol coulometrically?
  5. Bring out the difference between Voltametric and potentiometric methods of analysis.
  6. Explain the role of supporting electrolyte in polarography.
  7. Explain why photoemission occurs at higher wave length than absorption.
  8. What do you mean by carrier gas in GC? Give an example.

 

PART – B

Answer any EIGHT  questions.                                                                       (8×5=40 marks)

 

  1. Calculate the concentration of Ce+4 and Fe+2 in the mixture containing 20.00 mL of

0.100  N  Fe+2 and 40.00 mL of 0.0500 N Ce+4 in acidic medium.  E= 1.44 V and E= 0.77 V.

  1. What are metallochromic indicators? Give an example with the structure.  What are its characteristics?
  2. How is an outlier rejected using Q-test.
  3. Calculate the value of pZn in the mixture containing (I) 50.00 mL of 0.015 M Zn+2 and 30.00 mL of 0.025 M EDTA (ii) 50.00 mL of 0.025 M Zn+2 and 50.00mL of 0.050 M EDTA, both at pH 10.
  4. Write a note on Von Weimarn’s theory.
  5. Calculate the pH at which Mg(OH)2 begins to precipitate from 0.1000 Mg(NO3)2.

Ksp  of Mg(OH)2 = 1×10-11.

  1. What is DTGA? Compare it with DSC.
  2. What do you men by steam distillation? What are the condition for a compound to be steam distilled?
  3. A 0.5 millimolar solution of a divalent metal ion solution has diffusion current of 4 m The dropping rate of Hg was 24 drops½min.  The mass of 40 drops was found to be 15 mg.  Calculate the diffusion coefficient of the ion.
  4. a) Explain the mechanism phosphorescence.
  5. b) Explain the effect of the following on the intensity of fluorescence. (i) solvent (ii) pH

(iii) Dissolved oxygen.

  1. Interpret the DTGA pattern of an inorganic compound with a suitable example.
  2. a) Explain the principle of solvent extraction.
  3. b) Obtain an expression for the amount of substance extracted at the end of nth extraction

using small volume of the extracting solvent each time.

 

PART – C

Answer any FOUR  questions.                                                                        (4×10=40 marks)

 

  1. Give a critical account of acid base titrations in non-aqueous solvents.
  2. a) A 1.0000g sample containing Na2C2O4 requires 00 mL of 0.0200 M KMnO4 the for

oxidation in acid medium.  Calculate the percentage of Na2C2O4  in the sample and

express it scientifically.

  1. b) A blood sample is sent to two different laboratories to be analyzed for cholesterol. The

results obtained for the concentration (mg/dL) were:

Laboratory I               Laboratory II

= 243                      = 258

s1 = 13                         s2   = 15

n1 = 11                         n2   = 11

  1. Are the standard deviations significantly different at the 95% level?
  2. Are the two means significantly different at the 95% level?

F value at 95% probability level for the above set corresponds to 2.98.  Students ‘t’

value at 95% probability level is 2.26.

  1. a) What are the advantages and disadvantages of organic reagents in gravimetry?
  2. b) A 0.3500 g sample containing KCl and KI gives a precipitate of AgCl and AgI that

weighs 0.2720 g.  A 0.5250 g sample of the same material is titrated with 0.1020 M

AgNO3 requiring 25.80 mL.  Calculate the percentages of KCl and KI in the sample.

  1. a) What is the difference between electro-gravimetric method and Coulometric method.
  2. b) Explain the analytical method involved in the estimation Cu+2 by
  3. Electro gravimetric method
  4. Polarographic method
  5. a) Give the schematic representation of different types of variation of applied potential as

a function of time adopted in voltametry

  1. b) Write a note on cyclic voltametry.
  2. a) Draw the absorption, fluorescence and phosphorescence spectrum of a typical

compound.

  1. b) Give the schematic diagram of a spectroflurometer and explain the components.

 

 

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Loyola College M.Sc. Chemistry April 2006 Organics Substitution,Addition & Elimination Rxn Question Paper PDF Download

LM 29

             LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

SECOND SEMESTER – APRIL 2006

                     CH 2808 – ORGANIC SUBSTITUTION, ADDITION & ELIMINATION RXN

 

 

Date & Time : 19-04-2006/FORENOON     Dept. No.                                                       Max. : 100 Marks

Part-A

                                                    Answer ALL questions.      (10 ´ 2 = 20)

  1. Predict the product with mechanism
  2. What is ipso attack? Give the possible mechanism for ipso attack.
  3. What are stable, persistent and inert free radicals? Give example.
  4. Predict the product of the reaction of dihydropyran with primary alcohols in the presence of acids with mechanism.
  5. Predict the product.
  6. How would you explain that trans-2-acetoxycyclohexyl brosylate with acetate in glacial acetic acid gives only trans diacetate?
  7. Explain Grunwald-Winstein equation.
  8. Which of the following is more nucleophilic? Why?                                                       Benzene or mesitylene;  Phenoxide or p-nitrophenoxide
  9. Explain Hofmann’s rule in elimination reactions with a suitable example.
  10. What are ambident nucleophiles? Give an example.

PART B

Answer any EIGHT questions                        (8 ´ 5 = 40)

  1. Give the mechanism of the following:
  1. a) Wohl-Ziegler bromination          b)Wittig rearrangement.
  2. a) Predict the product with mechanism
  3. b) Explain Bartons reaction.
  4. Give the mechanism of oxymercuration reaction. Also give the evidences for the free radical mechanism for the cleavage of Hg.
  5. Predict the product with mechanism and evidence.
  6. Define isoinversion. Explain using a suitable example.
  7. Using suitable resonance-stabilizing structures explain why halogens are deactivators but o, p-directors.
  8. How would you show that the transition state in SN2 reaction must be linear?
  9. Threo DL pair of 3-bromo-2-butanol with HBr gave DL-2,3-dibromobutane while the erythro pair gave meso isomer. Explain.
  10. Explain ion-pair mechaism. What are its evidences?
  11. ‘Basic hydrolysis of a-bromopropionate ion with concentrated base gives a product with inverted configuration but with dilute base, retention product is formed’. Explain.
  12. What happens when the following are subjected to pyrolysis?
    (i) 2-acetoxybutane     (ii) Xanthate from isobutyl alcohol
  13. Solvolysis in acetone-water at 85°C of syn-7-p-anisyl-anti-7-norborn-2-enyl p-nitrobenzoate was only 2.5 times faster than that of the saturated compound’.

PART C

Answer any FOUR questions                   (4 ´ 10 = 40)

  1. How are the following synthesized from benezene?
    a) m-nitroacetophenone b) p-chlorobenzoic acid
    c)p-propylbenzen sulphonic acid                       d) m-bromopropylebenzene.
  2. a) How are the following conversions effected?
  3. b) Propose a synthesis for the following compounds using Robinson annulations.
  4. a) Give the mechanism of free radical substitution at an aromatic substrate. Substantiate it with suitable evidences.
    b) 2,3-dimethylbutane gives different ratio of products in aliphatic and aromatic solvents. Why?
  5. a) Endo-anti-tricyclo[3.2.1.02-4]octan-8-yl-p-nitrobenzoate is solvolysed about 1014times faster than p-niotro isomer containing C=C’. Explain.
  6. b) How would you show by reactions the mechanistic border line region between SN1 and SN2 reactions?
  7. a) Solvolysis of L-threo-3-phenyl-2-butyltosylate in acetic acid gives threo product in major amount’. Explain.
  8. b) What is ‘Product spread’ in elimination reactions? Explain with suitable examples.
  9. a) Explain Bucherer reaction with mechanism.
  10. b) Expalin the following:
    (i)     Acetolysis of both 4-methoxy-1-pentylbrosylate and 5-methoxy-2-pentylbrosylate give                    the same mixture of products.
  • Both erythro- and threo-1-acetoxy-2-deutero-1,2diphenylethane on pyrolysis give the same product.

 

 

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